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Fixation modes of gold(III) from solutions using cadmium(II) dithiocarbamates. Preparation, supramolecular structure and thermal behaviour of polynuclear and heteropolynuclear gold(III) complexes: Bis(N,N-dialkyldithiocarbamato-S,S′)gold(III) polychlorometallates, [Au(S2CNR2)2]nX (n=1: X=[AuCl4]−; n=2: X=[CdCl4]2−, [Cd2Cl6]2−)
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Rodina, Tatyana A., Ivanov, Alexander V., Gerasimenko, Andrey V., Loseva, Olga V., Antzutkin, Oleg N. and Sergienko, Valentin I.. (2012) Fixation modes of gold(III) from solutions using cadmium(II) dithiocarbamates. Preparation, supramolecular structure and thermal behaviour of polynuclear and heteropolynuclear gold(III) complexes: Bis(N,N-dialkyldithiocarbamato-S,S′)gold(III) polychlorometallates, [Au(S2CNR2)2]nX (n=1: X=[AuCl4]−; n=2: X=[CdCl4]2−, [Cd2Cl6]2−). Polyhedron, Vol.40 (No.1). pp. 53-64. ISSN 0277-5387
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Official URL: http://dx.doi.org/10.1016/j.poly.2012.03.043
Abstract
Four novel heteropolynuclear and polynuclear complexes of the general formulae [Au(S2CNR2)2]2X (X = [CdCl4]2−, R = CH3 (1); X = [Cd2Cl6]2−, R = C3H7 (2)) and [Au(S2CNR2)2][AuCl4] (R = iso-C3H7 (3); R = iso-C4H9 (4)) were prepared using heterogeneous reactions between appropriate freshly precipitated binuclear cadmium(II) dialkyldithiocarbamates and AuCl3 in 2 M hydrochloric acid. The isolated complexes were studied by 13C CP/MAS NMR spectroscopy, single-crystal X-ray diffraction and simultaneous thermal analysis (STA) under an argon atmosphere. In all molecular structures (1–4), one of the gold atoms coordinates two dialkyldithiocarbamate ligands in the S,S′-bidentate mode, forming a square-planar coordination polygon [AuS4], while the other gold atom (in 3 and 4) has four neighbouring chlorine atoms [AuCl4]. At the supramolecular level, compounds 1 and 2 comprise binuclear cations, [Au2{S2CN(CH3)2}4]2+ and polynuclear chains, ([Au{S2CN(C3H7)2}2]+)n in a combination with [CdCl4]2− and [Cd2Cl6]2− anions, respectively. Unexpected structural distinctions at the supramolecular level were discovered for the chemically related compounds 3 and 4. In these ionic complexes, there are either cationic trinuclear formations, {[Au{S2CN(iso-C3H7)2}2]2[AuCl4]}+, or polynuclear chains, ([Au{S2CN(iso-C4H9)2}2]+)n, both combined with [AuCl4]− anions, in the structural basis of compounds 3 and 4, respectively.
| Item Type: | Journal Article |
|---|---|
| Divisions: | Faculty of Science > Physics |
| Journal or Publication Title: | Polyhedron |
| Publisher: | Pergamon |
| ISSN: | 0277-5387 |
| Date: | 19 June 2012 |
| Volume: | Vol.40 |
| Number: | No.1 |
| Page Range: | pp. 53-64 |
| Identification Number: | 10.1016/j.poly.2012.03.043 |
| Status: | Peer Reviewed |
| Publication Status: | Published |
| Access rights to Published version: | Restricted or Subscription Access |
| URI: | http://wrap.warwick.ac.uk/id/eprint/49291 |
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